JPH04318047A - Vinyl chloride-based resin composition for coating electric wire - Google Patents

Abstract

PURPOSE:To provide a chlorinated vinyl chloride-based resin composition for coating electric wires, excellent in heat resistance, transparency and colorability and improved in electrical insulating properties with hardly any foaming in processing and forming. CONSTITUTION:A vinyl chloride-based resin composition for coating electric wires of this invention is obtained by adding (a) 0.05-10 pts.wt. metallic salt (without including a lead salt) of an organic carboxylic acid, phenols or organic phosphates, (b) 0.01-10 pts.wt. inorganic compound selected from hydrotalcite compounds and zeolite compounds and (c) 0.01-10 pts.wt. calcium oxide to 100 pts.wt. vinyl chloride-based resin.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a vinyl chloride resin composition for covering electric wires, and more specifically, it contains a metal salt of an organic carboxylic acid, a phenol, or an organic phosphoric acid, a hydrotalcite compound or a zeolite compound, and calcium oxide. The present invention relates to an agricultural vinyl chloride resin composition for covering electrical wires which has excellent thermal stability, coloring properties and electrical insulation properties by adding the additives, and which does not foam during molding.

0002

[Prior Art and Problems to be Solved by the Invention] Vinyl chloride resin is a general-purpose resin that is used in a wide range of applications, and is particularly characterized by excellent transparency and electrical insulation properties. It is widely used for coating purposes.

[0003] However, vinyl chloride resins have poor stability against heat and light, and have the disadvantage that they tend to undergo thermal decomposition mainly due to dehydrochlorination when subjected to thermoforming processing. In order to avoid such disadvantages, one or more types of thermal stabilizers have been added to suppress thermal deterioration during processing steps. Especially in the case of vinyl chloride resin for wire coating,
Stabilizers such as lead compounds have been used because of their properties such as electrical insulation, colorability, and thermal stability.

However, for example, in applications where transparency is required or where sulfide contamination is a problem, the above lead-based stabilizers cannot be used, and organic acids such as barium, magnesium, calcium, zinc and other metals cannot be used. Used in combination with salt. However, compared to the case where a lead-based stabilizer is used, the thermal stability is extremely poor, resulting in discoloration of processed products and a decrease in mechanical strength.

[0005] In order to improve these drawbacks, various stabilizing aids have been proposed, but it has been found that heat resistance can be improved to some extent by adding inorganic compounds such as hydrotalcite compounds or zeolite compounds. Be looked at. However, these inorganic compounds such as hydrotalcite compounds and zeolite compounds have water of crystallization in their molecules, which causes the problem of foaming during molding. There has been a strong desire to find an additive composition for vinyl chloride resin for covering electric wires that suppresses foaming.

[0006]

[Means for Solving the Problems] As a result of intensive studies in view of the above-mentioned current situation, the present inventors have found that by using a combination of specific additives, vinyl chloride resin can be improved in thermal stability, transparency, and The inventors have discovered that they have excellent coloring properties, less foaming during processing and molding, and excellent electrical insulation properties, which are improved to a level that is practically satisfactory, and have thus arrived at the present invention.

That is, the present invention provides vinyl chloride resin 10
0 parts by weight, (a) metal salts of organic carboxylic acids, phenols, or organic phosphoric acids (however, excluding lead salts)
0.05 to 10 parts by weight, (b) 0.05 to 10 parts by weight, (b) an inorganic compound selected from hydrotalcite compounds and zeolite compounds;
01 to 10 parts by weight and (c) calcium oxide 0.01
The object of the present invention is to provide a vinyl chloride-based resin composition for covering electric wires, in which 10 parts by weight of the vinyl chloride resin composition is added.

The vinyl chloride resin composition of the present invention will be explained in more detail below.

[0009] The metals constituting the metal salt of the organic carboxylic acid, phenol or organic phosphoric acid as component (a) used in the present invention (but not including lead) include lithium, potassium, sodium, calcium and barium. , magnesium, strontium, zinc, tin, cesium, aluminum, or organic tin.

[0010] Examples of the organic carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, neodecanoic acid, capric acid, undecanoic acid, and lauric acid. , tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3, 5-ditert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N,N-dimethylaminobenzoic acid, acetoxybenzoic acid, Monohydric carboxylic acids such as salicylic acid, p-tertiary octylsalicylic acid, elaidic acid, oleic acid, linoleic acid, linoleic acid, thioglycolic acid, mercaptopropionic acid, octylmercaptopropionic acid; oxalic acid, malonic acid, succinic acid, glutaric acid Acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, hydroxyphthalic acid, chlorphthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itacone acids, dicarboxylic acids such as aconitic acid and thiodipropionic acid, or their monoesters or monoamide compounds; Examples include di- or triester compounds of monovalent or tetravalent carboxylic acids.

Examples of the above-mentioned phenols include tertiary-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol, and isoamylphenol. Examples include octylphenol, 2-ethylhexylphenol, tertiary nonylphenol, decylphenol, tertiary octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol, methylisofxylphenol, and methyltertiary octylphenol.

The organic phosphoric acids mentioned above include mono- or di-octyl, -decyl, -dodecyl, -tridecyl, -tetradecyl, -hexadecyl, -octadecyl, -phenyl, -tolyl, -xylyl, -octylphenyl, - Examples include nonylphenyl phosphoric acid, pyrophosphoric acid, and phosphorous acid.

The amount of these metal salts of organic carboxylic acids, phenols or organic phosphoric acids added is 10% of the vinyl chloride resin.
The amount is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight.

The hydrotalcite compound as component (b) has the general formula Mg1-x Alx (OH
)2 A x/2 ・mH2O (I) (In the above formula, x is a real number in the range of 0<x≦0.5, and A is CO
3 or SO4, and m represents a real number. ) is a hydrous double salt compound consisting of magnesium and aluminum.

[0015] The hydrotalcite compound may be a natural product or a synthetic product. As for the synthesis method, Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-3
Examples include known methods described in Japanese Patent Publication No. 0039, Japanese Patent Publication No. 51-29129, and the like. Further, in the present invention, it can be used without being restricted by its crystal structure, crystal particle size, etc.

The surface of the hydrotalcite compound may be coated with higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal oleate, organic sulfonic acid metal salts such as alkali metal dodecylbenzenesulfonate, higher fatty acid amides, Those coated with higher fatty acid esters or wax can also be used.

Furthermore, compounds in which part of the metal in the hydrotalcite compound is replaced with other metals such as zinc can also be used.

The zeolite compound is an aluminosilicate having a unique three-dimensional zeolite crystal structure, and representative examples include A-type, X-type, Y-type and P-type zeolites, monodenite, analcite, and soda. Wright group aluminosilicates, such as clinobutyrolite, erionite, and chabasite, and all or part of the Group Ia metals of these aluminosilicates are ion-exchanged using Group II or Group IV metal ions. These zeolite compounds may be either hydrated compounds having water of crystallization (so-called zeolite water) or anhydrous compounds from which water of crystallization has been removed.

The amount of these hydrotalcite compounds or zeolite compounds added is 10% of the vinyl chloride resin.
The amount is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight.

[0020] Furthermore, component (c) calcium oxide is
It is also possible to use the white powder obtained by igniting limestone, calcium carbonate, hydroxide, nitrate, etc., as it is, but since moisture generates heat, for example,
It is preferable to use it in the form of a paste or wet powder by adding fatty acids, plasticizers, process oil, etc.

The amount of calcium oxide added depends on the moisture content of the vinyl chloride resin composition containing other additives, but is usually 0.01 to 10 parts by weight per 100 parts by weight of the vinyl chloride resin. Parts by weight, preferably 0.05-5
Parts by weight.

[0022]Although the components (a) to (c) used as stabilizers in the composition of the present invention can be separately blended into the vinyl chloride resin when blending, it is also possible to mix these components together. In this case, it can also be used as a so-called composite stabilizer containing other stabilizers or auxiliary components as required.

Examples of the vinyl chloride resin used in the present invention include polyvinyl chloride, pentachlorinated polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, and chlorinated polyvinyl chloride. Vinyl-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-alkyl chloride , cycloalkyl or arylmaleimide copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene polymer, vinyl chloride-isoprene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, chloride Vinyl-acrylic ester copolymer, vinyl chloride-
Vinyl chloride resins such as maleic ester copolymers, vinyl chloride-methacrylic ester copolymers, vinyl chloride-acrylonitrile copolymers, vinyl chloride-urethane copolymers, and the above-mentioned vinyl chloride resins and polyethylene,
α-olefin polymers such as polypropylene, polybutene, poly-3-methylbutene, polyolefins such as ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, and these copolymers, polystyrene, acrylic resin, styrene and other copolymers with monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.),
Acrylonitrile-butadiene-styrene copolymer, methacrylic acid ester-butadiene-styrene copolymer,
Examples include blended products with polyurethane.

The composition of the present invention may also contain other stabilizers, plasticizers and other additives that are normally used in vinyl chloride resin compositions for coating electric wires.

Other stabilizers that can be used in combination with the composition of the present invention include inorganic metal compounds, epoxy compounds, organic phosphite compounds, pure organic stabilizing aids, and the like.

Examples of inorganic metal compounds include oxides, hydroxides, carbonates, phosphates, pyrophosphates, chlorates, perchlorates, and hypochlorites of various metals.

The amount of these inorganic metal compounds added is 0.01 to 10 parts by weight per 100 parts by weight of the vinyl chloride resin.
Preferably it is 0.1 to 5 parts by weight.

Epoxy compounds include bisphenol type and novolac type epoxy resins, epoxidized natural oils and fats such as epoxidized soybean oil and epoxidized linseed oil, and alkyl esters of epoxidized unsaturated fatty acids such as epoxidized tall oil fatty acid octyl. , alicyclic epoxy compounds such as vinylcyclohexene diepoxy.

The amount of these epoxy compounds added is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

Examples of the organic phosphite compounds include triphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(nonylphenyl)
Phosphite, tris (mono and dinonylphenyl) phosphite, diphenyldecyl phosphite, trioctyl phosphite, phenyldioctyl phosphite,
trioctyl phosphite, diisodecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(
2,6-ditert-butyl-4-methylphenyl)pentaerythritol diphosphite, tetra(tridecyl)bisphenol A diphosphite, tetra(C12-C1
5 mixed alkyl) bisphenol A diphosphite, hexa(tridecyl)-1,1,3-tris(3-tert-butyl-4-hydroxy-6-methylphenyl)butane triphosphite, diphenyl acid phosphite, bis(nonylphenyl) Examples include acid phosphite.

The amount of these organic phosphite compounds added is 0.01 to 10 parts by weight per 100 parts by weight of vinyl chloride resin.
Parts by weight, preferably 0.1 to 5 parts by weight.

Examples of the pure organic stabilizing aids include phenols such as bisphenol A and hydrogenated bisphenol A; polyhydric alcohols such as pentaerythritol, dipentaerythritol, dipentaerythritol adipate, mannitol, and sorbitol; Ester compounds or partial ester compounds; β-diketone compounds and metal salts thereof such as dibenzoylmethane, benzoylacetone, stearylbenzoylmethane, dehydroacetic acid; 2,6-dimethyl-1,4-dihydropyridine-3,5- Dicarboxylic acid didodecyl ester, 2
-Organic nitrogen-containing compounds such as phenylindole and melamine.

The amount of these pure organic stabilizing aids added is 0.001 to 5 parts by weight per 100 parts by weight of the vinyl chloride resin.
Parts by weight, preferably 0.005 to 3 parts by weight.

[0034] These other stabilizers can be used in combination of two or more depending on the purpose. Generally, it is preferable to use the composition of the present invention in combination with a metal salt of an organic acid/organophosphite compound.

As the plasticizer used in the present invention, any plasticizer commonly used for vinyl chloride resins can be used. For example, phthalate plasticizers such as dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate; dioctyl avipate, diisononyl adipate, diisodecyl adipate, di( Adipate plasticizers such as butyl diglycol) adipate; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri(isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, octyl tri(butoxyethyl) phosphate Phosphate plasticizers such as diphenyl phosphate; polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol,
1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, neopentyl glycol, etc. and dibasic acids such as oxalic acid, malonic acid, Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid,
Polyester plasticizer using azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc., and if necessary monohydric alcohol or monocarboxylic acid as a stopper, epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil , epoxidized fish oil, epoxidized tallow oil, epoxidized safflower oil, epoxidized methyl stearate, -butyl, -2-ethylhexyl, -stearyl ester, epoxidized polybutadiene, epoxidized tall oil fatty acid ester, epoxidized linseed oil fatty acid Epoxy plasticizers such as esters; others include tetrahydrophthalic acid plasticizers, azelaic acid plasticizers, sebacic acid plasticizers, stearic acid plasticizers, citric acid plasticizers, trimellitic acid plasticizers, etc. Can be mentioned.

If necessary, the composition of the present invention may contain, for example, an ultraviolet absorber, a light stabilizer, a crosslinking agent, a filler, a pigment, a foaming agent, an antistatic agent, a plate-out inhibitor, a surface treatment agent, and a lubricant. , flame retardants, fluorescent agents, photodegradants, fungicides, bactericidal agents, nonmetallic stabilizers, processing aids, mold release agents, and the like.

[0037]

[Example] Next, the stabilizing effect of the composition of the present invention will be specifically illustrated by Examples. However, the invention is not limited to the following examples.

Example 1 [Formulation]
Part by weight Vinyl chloride resin (degree of polymerization 1450)
100 phthalic acid,
Adipic acid/1,4-butylene glycol
call polyester

50 epoxidized soybean oil

5 Calcium carbonate
10
Clay #33
10
magnesium oxide
0.
3 barium stearate
1.8
zinc stearate
0.
7 inorganic compounds (Table 1)
1.
Calcium pentoxide*
1
．． 0tetra(C2-15 mixed alkyl)bisphenol A diphosphite
1.0 *
: “CMS#242” manufactured by Ohmi Chemical Industry Co., Ltd.

[0039] Using the above blend, knead it with a roll at 175°C to a thickness of 0.
．． A 7 mm sheet was prepared, and its thermal stability was measured at 180° C. by the Congo Red method in accordance with JIS K-6723. Also, stack this sheet and heat it to 170℃ x 5.
A sheet with a thickness of 1 mm was prepared by pressing for 15 minutes at 180° C., and the color difference (colorability) of each sheet was visually determined. In addition, we observed the generation of air bubbles in the press sheet, and also determined the volume resistivity (VR) at 30°C.
was measured. The results are shown in Table 1. In addition, in the table, each test result is relatively expressed by ○, Δ, ×, and XX in descending order of favorable.

[0040]

[Table 1]

Example 2 [Formulation]
Part by weight Vinyl chloride resin (degree of polymerization 1300)
100 di-2-ethylhexyl phthalate
45 Epoxidized soybean oil

5 Bisphenol A diglycidyl ether 3 Calcium stearate
1.5 basic zinc octylate
1.0 dibenzoylmethane
0.05 Inorganic compounds (Table 2)
0.5 Calcium oxide*
1.5 diphenyl isodecyl phosphite
0.8 *: “CML#31” manufactured by Ohmi Chemical Industry Co., Ltd.

A test similar to that of Example 1 was conducted using the above formulation. In addition, the degree of haze is 170℃×
Pressing was performed for 5 minutes to create a pressed sheet with a thickness of 1 mm, and the sheet was measured with a haze meter. The results are shown in Table 2. In addition, in the table, each test result is ranked as ○,
Relatively expressed as △, ×, and XX.

[0043]

[Table 2]

From the above results, the vinyl chloride resin composition of the present invention has excellent thermal stability, thermal coloring properties, and transparency, prevents bubbles from forming in the press sheet, and has good electrical insulation properties. It is clear that it is also superior.

On the other hand, when calcium oxide is not used, or when hydrotalcite or zeolite is not used, air bubbles are generated in the press sheet, and vinyl chloride-based sheets are unsuitable for wire coating because of their poor thermal stability. It is a resin composition.

Furthermore, from the above results, the effects of the present invention are as follows:
It can be seen that a very specific effect is obtained by combining a metal salt, a hydrotalcite compound or a zeolite compound, and calcium oxide.

Effects of the Invention The vinyl chloride resin composition for covering electric wires of the present invention has excellent heat resistance, transparency, and coloring properties, less foaming during processing and molding, and excellent electrical insulation properties.

Claims (1)

[Claims] Claim 1: (a) metal salts of organic carboxylic acids, phenols, or organic phosphoric acids (excluding lead salts) 0.05 to 10 parts by weight of vinyl chloride resin;
(b) 0.01 to 10 parts by weight of an inorganic compound selected from hydrotalcite compounds and zeolite compounds; and (c) 0.01 to 10 parts by weight of calcium oxide. based resin composition.